Disazo dyes



UHTED STATES PATENT Q'FFIGE DISAZO DYES:

Swanie. S. Rossander, Wiimington, Del; and" Donovan E. Kvalnes, Penns Grove, N. JJ, as- Signors to E. I. du Pont de Nemours & Company, Wilmington; Del'., arcorporatiorrof-Delaware No Drawing. Application November 22, 1939, Serial No. 305,658

This invention relates to disazo dyes which are embodiments of the invention and not. as limidevoid of sulfonic acidand carboxyl groups and tationsthereof. Parts-areexpressedsinparts by which contain at least one polyhydroxyalkyl. Weight. group connected to an amino nitrogen; Example- 1 Heretofore attempts have been made to dye V i V A y cellulose acetate fibers with disazo dyes which g ig gg figgz 23 5835?; p ig' g g ggg are devoid of sulfonic acid and carboxyl groups. m-tro. anflineitonhydmxygethyl e-thyhanflmeand Such. dyes are gener a1 so insoluble-m Waiter; reducing .the nitrogroup-byhatihgwith sodium dlsperse' and t have sulfide; Were'dissolvedin1000pa-rts-of"Water and aifimty for the fiber that cellulose acetate fibers 300mm of 315% hydrochloric acid; cooled with cannot be satisfactorily dyed with them. Disazo ice to oo C anddiazotizedby. theqhdmmIofa dyes which are capable of satisfactorilydyeing' water solufion containing parts of Sodium cellulose acetate fibers are desired in order to nitrite The diam solutioh was their addd to provide a greater range of shades and other der V 1 8.80111171011 of 315 a t f sirable characteristics wh1ch are not provided by dine dissolved in 5 3 g fis g 'jgfi g gi a dyespartsof 31.5% hydrochloric acid. Mineral acid- 15 meets of esent Y itywas destroyed bythe slow addition of sodiumtion to provide disazo dyes whlc are deVOld 0f acetatesolution andcoupling was carried out at sulfomc acid and carboxyl groups and which aboutfllou Q The product f coupling was 1 ve ood affi y for va io s fibe s. especially latedzfroma .slightly alkalinemedium: It had for cellulose acetate fibers, and have other techgood mmt for. cellulose t t and dyed p nically valuable characteristics. Another objec lulose acetate fibers from Water solutions a bright of the invention is to provide such dyes which red shade.

contain at least one polyhydroxyalkyl group. The dye isrepresented by the formula.

. OCHz' 0211 orn HO 01H. 1 OHz(CHOH)4CHiO CH3 Another object of the invention is to provide Methyl; sorbityl cresidine wasobtained by disazo dyes which have good afiinity for cellulose condensing cresidine with glucose, catalytically acetate and which have other properties that reducingand"methylatingthe"sorbityl cresidine are necessary for making dye baths of practiwithdimethyl-sulfate;

cable technical value. Still other objects of the invention will be apparent from the following Example? description. I

The objects of the invention are attained in Threehundredand 'seven parts o-f-thecom general by eiiecting coupling of suitable compound obtained by coupling diazotized alphapounds which are devoid of sulfonic acid and naphthylamine to 2,5-dimethoXy-aniline; were carboxyl groups, either in a stepwise or single diazotizedin the same manneras describedin coupling reaction, and selecting the compounds Examplel and added to a solution made'by diswhich are coupled so that at least one composolving 223 parts of N-sorbit yl-1,5-amino-naph= nent of the product of coupling will contain a 5 thol in2000' parts of water and 100 parts of polyhydroxy radical connected to an amino ni- 1. hy och or d: e m l c ty trogen, the polyhydroxy radical being of the kind Wasslowlydestroyediby the addition of'sodiumwhich has 4 to 6 carbons and one less hydroxy acetate Solution; The coupling' was made" at than carbons of the monosaccharide aldose out and h product pli series. Dyeings are made from aqueous soluwas finally isolated from a neutral medium. The tions of the disazo compounds but some of the p oduct of c p s Soluble in water and disazo dyestufi may be present as a dispersion. dyeings were made on acetate silk from such soh n ti 111 b more fully t forth in lutions but more satisfactory dye baths were the following more detailed description which made by dispersing an excess of the compound includes examples that are given as illustrative in the solution. Satisfactory dyeings were made 2 on cellulose acetate fiber. blue shade.

The dyestufi is represented by the formula They were a bright Combination the component radicals. However, the secondary disazo compounds as represented by the scheme A B-+C are preferred.

Any diazotizable primary aryl amine which is devoid of sulfonic acid and carboxyl groups can be used as the first component in making the disazo compounds A B C of the invention. As illustrations of such primary aryl amines, the following are mentioned: aniline, o-, mand ptoluidine, 0-, mand p-chlor aniline, 2,5-dich1or aniline, o-, mand p-nitro amiline, 0-, mand panisidine, o-, mand p-phenetidine, o-chlor-pnitro-aniline, 4- and 5-nitro-2-amino-anisol, mand p-amino-acetanilide, p-amino-sorbityl-aniline, alpha and beta naphthylamine, 2,5-dimeth- Shade Para-amino-acctanilidc Ortho-chlor-aniline ortho-toluidine methyl, sorbityl-aniline. Ortho-chlor-aniline ortho-toluidine S0fblty10l'eS1 dlHe-. Ortho-ehlor-aniline ortho-toluidine methyl, sorbitylcresi Para-nitro'aniline meta-toluidine sorbityl-meta-toluidmer Ortho-chlor-aniline 2,5-dimethoxy-an1lme N-sorbityl-l,5-tlmmo-naphthol Para-phenetidine 2,5-dimethoxy-aniline N-sorbltyl-l,-am1no-naphthol 2,5-dimothoxy-aniline N-sorbityl-1,5-am1no-naphthol Dianisidine 2L(N-sorbityl-l,5-amino-naphth0l)]. N(para-amino-benzoyl) glucamine 2,5-dunethogzy-amlme phen Para-amino-sorbityl-aniline resorcin para-n 1tro;an1lme Para-aminosorbityl-aniline meta-phenylene-diamme N (para-ammo-benzoyl) gluon- Rcd brown. Greenish blue. Bluish green. Greenish blue. Reddish blue. Reddish orange.

Tan. Reddish brown.

21(para-nitro-aniline Tun.

Do. Orange. Yellow. Brown orange.

Violet.

Benzidinc (phenyl-glucamin eh Dianisidine (phcnyl-g mmmeh Yellow. Do.

Benzidine (methyl-sorbityl-anilinc)z.

The objects of the invention are attained when any polyhydroxyalkyl radical of the monosaccharide aldose series containing 4 to 6 carbons and one less hydroxy than carbons is contained in at least one of the radicals of the disazo compound and the polyhydroxyalkyl radical is connected to an amino nitrogen. As illustrations of such compounds are the erythrityl penta-erythrityl [--CH2C(CHzOI-I)al, arabityl [CH2(CI-IOH) CI-IzOH] fructyl (CHOH):-CH2OH and mannityl [--CH2(CHOH)4CH2OH] derivatives corresponding to the sorbityl and glucamine radicals recited in the foregoing illustrations, as for example methyl-penta-erythrityl-cresidine, methyl-fructyl-cresidine, penta-erythrityl-cresidine, N arabityl 1,5 amino naphthol, para amino-erythrityl-aniline, 1,6-dianilido-arabitol and the N (para-amino-benzoyl) amine of erythrose.

The couplings can be efiected in a variety of Ways as will be understood by those skilled in the art depending on the nature of the compounds employed and the position and number of polyhydroxyalkyl groups desired in the disazo product. For example where A, B and C represent the order in which the compounds are coupled,

oxy aniline, p-chlor-o-toluidine, the xylidines, cresidine, p-amino benzyl trimethyl ammonium bromide, N(p-amino benzoyl) glucamine, N(pamino benzoyl) methyl glucamine, N(mand pamino benzyl) methyl glucamine, N(mand pamino benzene sulfonyl) glucamine and p-amino sorbityl aniline.

As illustrations of the B component, the following are mentioned: aniline, oand m-toluidine, oand m-anisidine, oand m-phenetidine p-xylidine, cresidine, 2,5-dimethoxy-aniline, 2-methoxy-5-acety1 amino aniline, alpha and beta naphthylamine, m-amino acetanilide and N(m-amino-benzyl) methyl glucamine.

As the C component in such a disazo dye the following are mentioned as illustrative: aniline, oand m-toluidine, oand m-anisidine, oand m-phenetidine, p-xylidine, 2,5-dimethoxy aniline, 2-meth0xy-5-acetylamino aniline, m-amino acetanilide, alpha and beta naphthylamine, cresidine and 1,5-amino naphthol. All of the above products and their secondary and tertialy amines wherein the N-groups are alkyl, hydroxyalkyl and polyhydroxyalkl containing 4 to 6 carbons and one less hydroxy than carbons, such as methyl, sorbitylaniline, sorbityl alpha naphthylamine, hydroxy ethyl, sorbityl m-toluidine, di(hy droxy ethyl) aniline, ethyl hydroxy ethyl aniline, and others such as resorcin, m-phenylene diamine, diphenylamine and N-sorbityl m-phenylene diamine can be used.

In compounds C being the last, a variety of methods can be em- 0 ployed such as A B C, A- B+C, B A+C, and G J 7 0 A\ the C components of the foregoing compounds 0 A B C are suitable. Suitable A compounds are and the polyhydroxyalkyl group or groups may be present in any one, in any two or in all of those having two primary amine groups such as benzidine, dianisidine, toluidine mand p-phenylene diamine (made by an indirect method of droxyalkyl bridging group. of 4Ito 6 carbons and one less hydroxy than carbons.

Combinations such as B+A C can be made by di'azotizing a primary arylamine which 'iSLSllbsti-tutedby a nitro or a hydrolyzable acylamino group, coupling to a C compound such as ethyl; hydroxy ethyl aniline, reducing or hydrolyzing the monazo compounds, as the case may be, to produce a primary amino group connected to A, and finally diazotizing and coupling to a coupling component, such as a B or C component of the combination A B C. Illustrations: of compounds A in B A C are those such as pm'tro aniline, oxalyl p-phenylene diamine, formyl m-phenylene diamine. By suitable use of intermediates of the kinds mentioned a great variety of disazo compounds containing at least one of the described polyhydroxyalkyl groups connected to an amino nitrogen can be made.

In general the disazo compounds which contain sulfonic acid and carboxyl are soluble but they lack afiinity for cellulose acetate fiber while those which are devoid of such groups and con-' tain other substituents besides the described polyhydroxyalkyl groups are insoluble. Dispersions of most of the latter compounds lack afiinity or'produce poor dyeings on acetate silk, and those which show any affinity for cellulose acetate fiber when dispersed make dye baths having unsatisfactory characteristics, such as exhaust value. However, the presence of the described polyhydroxyalkyl groups in the disazo compounds which are devoid of sulfo and carboxyl groups gives compounds having satisfactory solubility, dispersibility, aflinity and other characteristics necessary for satisfactory and improved dyeings on acetate silk and for satisfactory preparation and operation of the dye baths. As far as we are aware, the dyes disclosed are more soluble in water, are more readily dispersed in water solutions of the dyes, are more readily applied to the fiber than any disazo dye heretofore known.

From the foregoing disclosure it will be recognized that the invention is susceptible of modification without departing from the spirit and scope thereof and it is to be understood that the invention is not restricted to the specific illustrations thereof herein set forth.

We claim:

1. A disazo dyestuff represented by the formula in which each R is one of a group consisting of benzene and naphthalene nuclei; X is from the group consisting of hydrogen, methyl, alkoxy containing 1 to 4 carbons, nitro, halogen, hydroxy, amino, acetylamino, --NI-I polyhydroxyalkyl,

alkyl polyhydroxyalkyl i N/alkyl polyhydroxyalkyl wherein polyhydroxyalkyl has 4 to 6 carbons and one. less hydroxy, than carbons and the alkyl groups haveltox l'carbons; R is one of agroup consisting of the radicals Benzene Y wherein Y is from the group consisting of hydrogen, methyl, alkoxy having 1 to 4 carbons, halogen,1...hydroxy, amino; acetylamino, NH- polyhydroxyalkyl;

polyhydroxyalkyi and wherein polyhydroxyalkyl is from the monosaccharide aldose series and has 4 to--6carbons and oneless hydroxythancarbons and-the alkyl groups have1 to 4--carbons; n is an integer" not greater-than 2 and Q-is-one of the group consisting ofl'CH=CH, NH, O--, S-, SO2-.,.,CO, -CH2, and NILpolyhydroxyalkyl-NH, said dyestufi having at least one polyhydroxyalkyl amino group; said compound being. devoid .of-a nuclearlyr substituted tertiary amino group when one-R is the nucleus of a naphthol.

2. The secondary disazo dyestuffs represented by the formula in which each R is one of a group consisting of benzene and naphthalene nuclei, X is from the group consisting of hydrogen, methyl, alkoxy containing 1 to 4 carbons, nitro, halogen, hydroxy, amino, acetylamino, NI-I polyhydroxyalkyl,

alkyl N/ polyhydroxyalkyl and 0 alkyl my polyhydroxyalkyl wherein polyhydroxyalkyl has 4 to 6 carbons and i one less hydroxy than carbons and the alkyl groups have 1 to 4 carbons; R is one of a group consisting of the radicals Benzene and wherein Y is from the group consisting of 5. The compound represented by the formula OCH:

6. The process which comprises diazotizing a primary aryl amine of the benzene series; coupling with a compound of the benzene series my] containing one of a group consisting of amino and a group capable of being transformed into 15 amino after coupling, and coupling the diazo hydrogen, methyl, alkoxy having 1 to 4 carbons, 10 halogen, hydroxy, amino, acetylamino, --NH- polyhydroxyalkyl,

p y y y y derivative of said monazo compound with a comand pound of the benzene series, said compounds 0 alkyl being devoid of carboxy and sulfonic acid groups and at least one of said compounds containing 20 one of a group consisting of -NH polyhydroxypolyhydroxyalkyl y wherein polyhydroxyalkyl is from the .monoa yl saccharide aldose series and has 4 to 6 carbons and one less hydroxy than carbons and the alkyl groups have 1 to 4 carbons; n is an integer not 25 yhyd oxyalkyl greater than 2 and Q is one of the group conand sisting of CH=CH, -NH, -O-, S, 0 1k 1 4502-, -co-, -CH2-, and NH-po1y- H hydroxyalkyl-NH, said dyestufi having at least one polyhydroxyalkyl amino group, said com- 30 polyhydl-oxyalkyl pound being devoid of a nuclearly substituted tertiary amino group when one R is the nucleus of a naphthol.

3. The compound represented by the formula 4. The compound represented by the formula SWANIE s ROSSANDER.

OCH; DONOVAN E. KVALNES.

wherein polyhydroxyalkyl has 4 to 6 carbons and one less hydroxy than carbons and alkyl has 1 to 4 carbons. 

